Fe Oxyhydroxides Research Articles

Extreme iron cycling in a coastal lake-lagoon system driven by interactions between climate and entrance management

Intermittently closed and open coastal lakes and lagoons (ICOLLs) are ecologically important and hydrologically sensitive estuarine systems. We explore how extreme drought and ICOLL entrance management intersect to influence the geochemical cycling of iron. Opening the ICOLL entrance just prior to an extreme drought in 2019 led to prolonged extremely low water levels, thereby exposing intertidal/subtidal sulfidic sediments and causing oxidation of sedimentary pyrite. Subsequent reflooding of exposed sediments for ∼4 months led to extremely elevated Fe2+(aq) (>10 mM) in intertidal hyporheic porewaters, consistent with Fe2+(aq) release via pyrite oxidation and via reductive dissolution of newly-formed Fe(III) phases. Re-opening the ICOLL entrance caused a rapid fall in water levels (∼1.5 m over 7 d), driving the development of effluent groundwater gradients in the intertidal zone, thereby transporting Fe2+-rich porewater into surface sediments and surface waters. This was accompanied by co-mobilisation of some trace metals and nutrients. On contact with oxic, circumneutral-pH estuarine water, the abundant Fe2+(aq) oxidised, forming a spatially extensive accumulation of poorly crystalline Fe(III) oxyhydroxide floc (up to 25 % Fe dry weight) in shallow intertidal zone benthic sediments throughout the ICOLL. Modelling estimates ∼4050 × 103 kg of poorly-crystalline Fe was translocated into surficial sediments. The newly formed Fe(III)-oxyhydroxides serve as a metastable sink encouraging enrichment of both phosphate and various trace metal(loid)s in near-surface sediments, which may have consequences for future cycling of nutrients, metals and ICOLL ecological function. The additional Fe also may enhance ICOLL sensitivity to similar future drought events by encouraging pyrite formation in shallow (<5 cm) benthic sediments. This system-wide translocation of Fe from deeper sediments into surficial benthic sediments represents a form of geochemical hysteresis with an uncertain recovery trajectory. This study demonstrates how climate extremes can interact with anthropogenic management to amplify ICOLL hydrological oscillations and influence biogeochemistry in complex ways.

A method for studying the influence of Mn oxyhydroxides on the trace element content of aquatic bryophytes

The main objective of this study was to develop and test a method of separating externally deposited Mn oxyhydroxides and co-precipitated elements from samples of aquatic moss (the moss Fontinalis antipyretica). The method, which uses 0.1 M hydroxylamine to dissolve the oxyhydroxides, was tested with samples collected in rivers with slightly acidic, well‑oxygenated waters, where high rates of Mn precipitation occur. The method was effective (it extracted up to 84 % of the Mn) and selective (Fe oxyhydroxides were not extracted). The elements Ba, Cd, Zn and Ni were associated with the Mn oxyhydroxides, while Al, As, Cr, Cu, Fe, Hg and Pb were not. Deposition of Mn therefore increased the concentration of some elements in the moss samples. However, as Mn precipitation depends on Eh and pH, which are independent of the concentrations of the elements in water, the relationship between water and moss element concentrations is not clear (i.e. the data are noisy). This is a problem in biomonitoring studies, which assume a close relationship between element concentrations in moss and water. The value of the proposed extraction method is that it can be used to correct the effect of Mn deposition. We present an example of this correction applied to the Cd concentrations in the test data. We found that the noise introduced by the Mn, including age-related effects (observed by comparing concentrations in 0–2.5 and 2.2–5.0 cm sections from the shoot apex), can be reduced. Additionally, the correction revealed recent increases in Cd concentrations in one site that were not observed in the uncorrected data. Another finding of interest was the low content of total Mn and different extractability (of most elements) observed in moss samples collected in alkaline waters. Finally, we discuss how future studies designed for different environmental scenarios can benefit from application of the proposed method.

Geostatistical assessment of groundwater arsenic contamination in the Padana Plain

Arsenic (As) in groundwater from natural and anthropogenic sources is one of the most common pollutants worldwide affecting people and ecosystems. A large dataset from >3600 wells is employed to spatially simulate the depth-averaged As concentration in phreatic and confined aquifers of the Padana Plain (Northern Italy). Results of in-depth geostatistical analysis via PCA and simulations within a Monte Carlo framework allow the understanding of the variability of As concentrations within the aquifers. The most probable As contaminated zones are located along the piedmont areas in the confined aquifers and in the lowland territories in the phreatic aquifers. The distribution of the As contaminated zones has been coupled with hydrogeological, geological, and geochemical information to unravel the sources and mechanisms of As release in groundwater. The reductive dissolution of Fe oxyhydroxides and organic matter mineralization under anoxic conditions resulted to be the major drivers of As release in groundwater. This phenomenon is less evident in phreatic aquifers, due to mixed oxic and reducing conditions. This large-scale study provides a probabilistic perspective on As contamination, e.g. quantifying the spatial probability of exceeding national regulatory limits, and to outline As major sources and drivers.

Sediment-redox dynamics in an oligotrophic deep-water lake in Tierra del Fuego: insights from Fe isotopes

For long time in the history of Earth, ferruginous conditions governed the oceans. With the rise of oxygen during the Proterozoic era and the subsequent evolution of living organisms, worldwide deposition of iron formations occurred. These sedimentary units reveal the transition into oxic oceans, passing by local and transitory euxinic conditions, especially in coastal shelves. Constraining the iron cycle and the biogeochemical processes occurring in present and past ferruginous basins helps answering some of the question regarding global oxygenation, the evolution of life and past climate changes. Therefore, Fe speciation and Fe isotopes in both Proterozoic and recent sedimentary records have been widely used to reconstruct past basin dynamics and redox conditions in the sediment–water interface. However, sedimentation and early diagenesis can alter paleoredox proxies and their primary climate signals. In this work, we disentangled alteration processes occurring at the redox front below the sediment–water interface of a ventilated deep-water lake (Lago Fagnano, Argentina/Chile). A sequential extraction protocol was applied to characterize two reactive Fe pools: Fe oxyhydroxides and reduced iron. Subsequently, Fe isotopes were constrained to determine the main processes mobilizing Fe. At the redox front, ferric minerals reach a δ56Fe value of − 1.3‰ resulting from oxidation of dissolved Fe likely following a Rayleigh distillation effect. Dissolved Fe is produced right below via Fe reduction, as shown by the low ferric Fe content. Our observations delineate a redox cycle and a redox horizon undergoing constant upward migration, initiated by regular sedimentation. However, during events of increased rapid sedimentation (e.g., seismites) this dynamic cycle is interrupted inducing full or partial preservation of the Fe-rich redox front. In such case, oxidation of dissolved Fe is interrupted and can be recycled in ferrous minerals, such as Fe monosulfides and amorphous phases with δ56Fe values down to − 1.7 ‰. These findings have significant implications for the recording of biogeochemical cycles in the geological past, the use of Fe isotopes in freshwater-lake sediments for paleoclimate studies, and the progress of our knowledge regarding the geochemistry of past oceans.

Incorporation of Shewanella oneidensis MR-1 and goethite stimulates anaerobic Sb(III) oxidation by the generation of labile Fe(III) intermediate

Dissimilatory iron-reducing bacteria (DIRB) affect the geochemical cycling of redox-sensitive pollutants in anaerobic environments by controlling the transformation of Fe morphology. The anaerobic oxidation of antimonite (Sb(III)) driven by DIRB and Fe(III) oxyhydroxides interactions has been previously reported. However, the oxidative species and mechanisms involved remain unclear. In this study, both biotic phenomenon and abiotic verification experiments were conducted to explore the formed oxidative intermediates and related processes that lead to anaerobic Sb(III) oxidation accompanied during dissimilatory iron reduction. Sb(V) up to 2.59 μmol L−1 combined with total Fe(II) increased to 188.79 μmol L−1 when both Shewanella oneidensis MR-1 and goethite were present. In contrast, no Sb(III) oxidation or Fe(III) reduction occurred in the presence of MR-1 or goethite alone. Negative open circuit potential (OCP) shifts further demonstrated the generation of interfacial electron transfer (ET) between biogenic Fe(II) and goethite. Based on spectrophotometry, electron spin resonance (ESR) test and quenching experiments, the active ET production labile Fe(III) was confirmed to oxidize 94.12% of the Sb(III), while the contribution of other radicals was elucidated. Accordingly, we proposed that labile Fe(III) was the main oxidative species during anaerobic Sb(III) oxidation in the presence of DIRB and that the toxicity of antimony (Sb) in the environment was reduced. Considering the prevalence of DIRB and Fe(III) oxyhydroxides in natural environments, our findings provide a new perspective on the transformation of redox sensitive substances and build an eco-friendly bioremediation strategy for treating toxic metalloid pollution.

INFLUENCE OF рН AND Ca&lt;sup&gt;2+&lt;/sup&gt; IONS ON CHEMICAL COMPOSITION AND SORPTION OF &lt;sup&gt;137&lt;/sup&gt;Cs BY CHERKASY BENTONITES (UKRAINE)

The safety of near-surface and deep radioactive waste storage facilities is based on a system of engineered and natural barriers. Significant degradation of the engineered barrier system composed of cemented waste matrixes covered by cement mixture, concrete compartments, and structures at the basement of the storage facility may cause radionuclide transfer from the facility to groundwater. Mixing of the cement and concrete with water leads to the formation of several various hydration products with subsequent leaching of Ca2+ ions and formation of hydroxyl ions (OH-), which affects the alkalinity of the water environment and the sorption properties of bentonite, as a component of the engineered barrier at the basement of near-surface facilities. The article presents the results of an experimental study of the influence of Ca2+ ion concentration and pH of the model solution (similar to groundwater composition at Vector Site in Chornobyl Exclusion Zone) on the elemental composition and sorption properties of natural (NB) and Na-modified (PBA-20) bentonites from the Cherkasy deposit concerning 137Cs at the Solid : Solution ratio of 1 : 100. Geochemical modeling suggests that addition of CaCl2 to test solution and resulting alkaline pH leads to precipitation of solids, mainly oxides, hydroxides, Fe oxyhydroxides (hematite, goethite, limonite), and Ca carbonates (calcite, aragonite, dolomite). Their role in Cs adsorption was evaluated. The concentration of structural elements (Si, Al) in bentonites practically does not change with Ca2+ ion concentration increase in the model solution, demonstrating the bentonite structure’s stability under these conditions. At the same time, an increase in the Ca concentration and a decrease in the Na concentration was found in the ion exchange complex of the bentonites if compared to the initial natural bentonite. This results in the transformation of Na-modified bentonite from Na, Ca-form to Ca, Na-form. The total sorption capacity of NB and PBA-20 bentonite concerning Cs+ ions at increased concentrations of Ca2+ ions and pH of the solution slightly decreases, though retaining high values of the degree of absorption (&gt; 90 %). The total adsorption of Cs+ ions on NB and PBA-20 bentonites from model groundwater with the addition of CaCl2 from 16 to 960 mg/dm3 and increase of рН from 7.4 to 11.8 decreases with the increase in ionic strength, in particular, due to competition with Са2+ and Na+ ions. NB and PBA-20 bentonites of the Cherkasy deposit remain a reliable component of the liner at the repository basement owing to their main functional property – high absorption capacity for 137Cs, which is an important dose-forming radionuclide of short-lived low- and medium-level waste.

Phototrophic Fe(II) oxidation benefits from light/dark cycles.

Phototrophic Fe(II)-oxidizers use Fe(II) as electron donor for CO2 fixation thus linking Fe(II) oxidation, ATP formation, and growth directly to the availability of sunlight. We compared the effect of short (10 h light/14 h dark) and long (2-3 days light/2-3 days dark) light/dark cycles to constant light conditions for the phototrophic Fe(II)-oxidizer Chlorobium ferrooxidans KoFox. Fe(II) oxidation was completed first in the setup with constant light (9 mM Fe(II) oxidised within 8.9 days) compared to the light/dark cycles but both short and long light/dark cycles showed faster maximum Fe(II) oxidation rates. In the short and long cycle, Fe(II) oxidation rates reached 3.5 ± 1.0 and 2.6 ± 0.3 mM/d, respectively, compared to 2.1 ± 0.3 mM/d in the constant light setup. Maximum Fe(II) oxidation was significantly faster in the short cycle compared to the constant light setup. Cell growth reached roughly equivalent cell numbers across all three light conditions (from 0.2-2.0 × 106 cells/mL to 1.1-1.4 × 108 cells/mL) and took place in both the light and dark phases of incubation. SEM images showed different mineral structures independent of the light setup and 57 Fe Mössbauer spectroscopy confirmed the formation of poorly crystalline Fe(III) oxyhydroxides (such as ferrihydrite) in all three setups. Our results suggest that periods of darkness have a significant impact on phototrophic Fe(II)-oxidizers and significantly influence rates of Fe(II) oxidation.

Phototrophic Fe(II) oxidation by Rhodopseudomonas palustris TIE-1 in organic and Fe(II)-rich conditions.

Rhodopseudomonas palustris TIE-1 grows photoautotrophically with Fe(II) as an electron donor and photoheterotrophically with a variety of organic substrates. However, it is unclear whether R. palustris TIE-1 conducts Fe(II) oxidation in conditions where organic substrates and Fe(II) are available simultaneously. In addition, the effect of organic co-substrates on Fe(II) oxidation rates or the identity of Fe(III) minerals formed is unknown. We incubated R. palustris TIE-1 with 2 mM Fe(II), amended with 0.6 mM organic co-substrate, and in the presence/absence of CO2 . We found that in the absence of CO2 , only the organic co-substrates acetate, lactate and pyruvate, but not Fe(II), were consumed. When CO2 was present, Fe(II) and all organic substrates were consumed. Acetate, butyrate and pyruvate were consumed before Fe(II) oxidation commenced, whereas lactate and glucose were consumed at the same time as Fe(II) oxidation proceeded. Lactate, pyruvate and glucose increased the Fe(II) oxidation rate significantly (by up to threefold in the case of lactate). 57 Fe Mössbauer spectroscopy revealed that short-range ordered Fe(III) oxyhydroxides were formed under all conditions. This study demonstrates phototrophic Fe(II) oxidation proceeds even in the presence of organic compounds, and that the simultaneous oxidation of organic substrates can stimulate Fe(II) oxidation.

Coupled carbon‑iron‑phosphorus cycling in the Rainbow hydrothermal vent field

Hydrothermal venting has been shown to play a role in the global biogeochemical cycles of three bio-essential elements: iron (Fe), carbon (C) and phosphorus (P). However, our insight into the coupled cycling of Fe and associated C and P in hydrothermal plumes as well as their long-term fate in the underlying sediments remains limited. We present a detailed study, tracing the biogeochemical pathways of hydrothermally sourced Fe and the associated C and P from a buoyant to a neutrally buoyant plume and to the underlying sediments. Combining chemical and micro(spectro)scopic methods, we characterize particulate and dissolved phases recovered from the water column and sediment at two sites: one located directly in the active Rainbow hydrothermal vent field at 36°N on the mid-Atlantic ridge (MAR) and one located 3 km NE of the active vents. Our results show that the precipitates in one of the largest hydrothermal plumes on the MAR consist of aggregates of Fe nanoparticles, comprising poorly-ordered Fe oxyhydroxides and polycrystalline Fe sulfides, coated with carbon that is likely of organic origin. The sediments underlying the hydrothermal plume show enrichments in organic C, Fe, P and vent-derived trace metals such as Cu that decrease with distance from active vents. The enrichment in organic C and persistence of apparently highly-reactive Fe phases after sediment burial may reflect enhanced preservation potential of both phases as a result of the formation of organic-mineral complexes. We further demonstrate that the scavenging of dissolved seawater phosphate (PO43−) by Fe nanoparticles is constrained to early stages of particle formation and sorption reactions in the buoyant hydrothermal plume and that P burial close to the vent field is driven by the deposition of the Fe nanoparticles. In the sediment, P is then efficiently retained through sink-switching from Fe-bound to more stable, authigenic apatite phases. As such, the sediments underlying the Rainbow vent seem to faithfully record coupled emission, scavenging and burial of essential elements and therefore offer potential for reconstruction of past venting activity. The deposition and burial of partly reduced plume material (e.g., Fe sulfides) in an oxic deep-sea sediment results in sediment chemistry and diagenesis that is very specific to the hydrothermal environment, while the redox signature of the plume is gradually lost. Beyond its role as a potential source of bioavailable Fe, we highlight how hydrothermal venting represents an efficient sink for organic C and bioavailable P. The findings contribute to understanding the profound impact of geological episodes of increased hydrothermal activity on ocean biogeochemistry and the coupled ocean-climate system.

Fe(III) oxyhydroxides mediated electron transfer from thiols to O2 for hydroxyl radical production

Thiols serve as important electron reservoirs in subsurface environments, playing an important role in biogeochemical cycling of redox-sensitive elements. Nevertheless, due to the kinetic constraint on thiol oxidation by O2, hydroxyl radical (•OH) production during thiol oxygenation had long been disregarded. •OH is the most powerful oxidant in natural environment, capable of oxidizing most of inorganic and organic pollutants. This study revealed that Fe(III) oxyhydroxides could mediate electron transfer from thiols to O2, thereby facilitating •OH production within a pH range of 3 to 9. For instance, at pH 7, the presence of 1 g/L ferrihydrite increased •OH accumulation from <0.2 to 15.3 μM within 10 h during the oxygenation of 6 mM cysteine. This enhancement resulted from Fe(III) oxyhydroxides altering the •OH production pathway from the direct oxidation of thiols by O2 to the oxidation of adsorbed Fe(II) by O2. In natural soils, Fe(III) oxyhydroxides were estimated to contribute to 69–81% of thiol removal and to 56–82% of •OH production. Furthermore, the •OH produced during thiol oxygenation also exhibited the capability to degrade phenol. This study highlights the previously overlooked catalytic role of Fe(III) oxyhydroxides in facilitating thiol oxidation and •OH production.

Influence of Cr(III) on the formation and transformation of corrosion products of steel in marine environments

A fundamental approach is used to better understand the influence of Cr on the resistance of low alloy steel to marine corrosion. It focuses on the formation and transformation of corrosion products of steel in seawater-like electrolytes. Fe(OH)2 precipitates are then prepared by mixing a solution of NaCl, Na2SO4·10H2O, FeCl2·4H2O or FeCl2·4H2O + CrCl3·6H2O (so that Cr = 8% and Fe = 92%), with a solution of NaOH. The initial concentration ratio of reactants, Q=frac{2[{{{rm{Fe}}}}^{2+}]+3[{{{rm{Cr}}}}^{3+}]}{[{{{rm{OH}}}}^{-}]}, is set at Q = 0.88, 1, and 1.136. In a first approach, the obtained aqueous suspension is stirred, at a controlled temperature of 25 ± 0.5 °C, to be oxidized by air. The resulting oxidation product is characterized by XRD and Raman spectroscopy. In a second approach, the Fe(OH)2 precipitates are aged one week in suspension in anoxic conditions, filtered, mixed as a wet paste with glycerol and set as a thin compact layer on the sample holder of a X-ray diffraction system. The oxidation process of Fe(OH)2 is then monitored in situ during the acquisition of the X-ray diffractogram. The obtained results demonstrate that Cr(III) hinders the formation of green rust compounds, hence hindering the formation of γ-FeOOH, i.e., the main oxidation product of green rust compounds. The other oxidation pathways of Fe(OH)2, which lead to Fe3O4 or α-FeOOH, are thus favored. Nevertheless, Cr(III) favors mainly the solid state transformation pathway of Fe(OH)2, thus promoting α-FeOOH via the formation of poorly ordered Fe(III) oxyhydroxides, namely feroxyhyte and ferrihydrite.

Evolution of Bentonites in the Presence of Ca2+ Ions in a Contact Solution and Sorption Capacity of Bentonites for 137Cs and 90Sr

The article presents the results of an experimental modelling of the influence of Са2+ ion concentration and pH of a model solution on the elemental composition and sorption capacity of natural (NB) and sodium-modified (SMB-20) bentonites from the Cherkasy deposit for 137Cs and 90Sr. The processes of the Cs and Sr sorption from multicomponent solutions with different pH, Eh and salt composition depend on the insoluble or sparingly soluble compounds precipitated on the bentonite surface. Based on the computer simulation data, it was found that small amounts of sediments, mainly oxides, hydroxides, Fe oxyhydroxides (hematite, goethite, limonite), and Ca carbonates (calcite, aragonite, dolomite) were present in the model solution with alkaline pH after adding CaCl2 solutions. Oxides and hydrated oxides of Fe, and calcium carbonates play an important role in the Cs and Sr sorption processes on bentonites. They can concurrently sorb radionuclides and block the sorption centres in montmorillonites. The concentration of the main structural elements (Si, Al) in the bentonites practically does not change with the increased pH and Ca2+ ion concentration in the model solution compared to the initial samples of NB and SMB-20, which indicates their structural stability. At the same time, an increase in the calcium concentration and a decrease in the sodium concentration were found in the ion-exchange complex of montmorillonite — the main bentonite mineral if compared to the initial samples. This can eventually lead to the transformation of SMB-20 bentonite from Na, Ca form to Ca, Na form. The 137Cs and 90Sr sorption on NB is shown to proceed more effectively, compared to SMB-20 in conditions of the increased pH and Ca2+ ion concentration. The results of this research may justify the bentonite clay application as a component of the isolating engineered barriers of radioactive waste disposal facilities.

Mineralogical fingerprint and human health risk from potentially toxic elements of Fe mining tailings from the Fundão dam

In 2015, >50 million cubic meters of Fe mining tailings were released into the Doce River basin from the Fundão dam, raising the question of its consequences on the affected ecosystems. This study aimed to establish a mineralogical-(geo)chemical association of potentially toxic elements (PTEs) from Fe mining tailings from the Fundão dam, collected seven days after the failure, through a multidisciplinary approach combining assessment of the risk to human health, environmental geochemistry, and mineralogy. Thus, eleven tailings samples were collected with the support of the Brazilian Military Police Fire Department. Granulometry, magnetic measurements, optical microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and sequential chemical extraction of PTEs analyses were performed. Contamination indexes, assessment of risk to human health, and Pearson correlation were calculated using the results of sequential chemical extraction of PTEs. The predominance of goethite in Fe oxyhydroxide concentrates from the mud indicates that the major source of hematite may not be from tailings, but from pre-existing soils and sediments, and/or preferential dissolution of hematite in deep flooded zones of the tailings column of the Fundão dam. Moreover, the high correlation of most carcinogenic PTEs with their crystallographic variables indicates that goethite is the primary source of contaminants. Goethites from Fe mining tailings showed high specific surface area and Al-substitution, and due to their greater stability and reactivity, the impacts on PTE sorption phenomena and bioavailability may be maintained for long periods. However, their lower dissolution rate, and the consequent release of heavy metals would promote greater resilience for affected ecosystems, preventing significant PTE inputs under periodic reduction conditions. More specific studies, involving the crystallographic characteristics of Fe oxyhydroxides should be developed since they may provide another critical component of this set of complex and dynamic variables that interfere with the bioavailability of metals in ecosystems.

Soil enzyme activities in heavily manured and waterlogged soil cultivated with ryegrass (Lolium multiflorum)

Extended waterlogging (WL) conditions can alter soil enzyme activities and their role in maintaining healthy soils. We assessed the effects of soil moisture regimes (field capacity [FC] and WL) and phosphorus (P) rates (0, 15, 30, 45 kg available P ha–1) on ( i) soil enzymes and microbial biomass carbon (MBC), microbial biomass nitrogen (MBN), and microbial biomass P (MBP); and ( ii) dissolved organic carbon (DOC) and total dissolved nitrogen (TDN). The treatments were tested in a 4-month greenhouse experiment using intact soil columns under annual ryegrass ( Lolium multiflorum). WL decreased the activity of β-glucosidase and acid phosphomonoesterase but increased N-acetyl-β-glucosaminidase in soils. These changes were associated with changes in MBC, DOC, MBN, and TDN, but not MBP. Anoxic conditions in WL soil promote the activity of anaerobes and contribute to the reduction of Fe oxyhydroxides and the release of DOC, TDN, and P in the soil solution. The activity of the extracellular enzymes decreased in WL with additions of slurry indicating adequate supply of C, N, and P. Our results also showed that both enzyme activities and microbial biomass were restricted in the upper soil layer with limited downward movement along the soil profile. We can conclude that since these enzymes control the hydrolysis of cellulose, phosphomonoester, and chitin, soil moisture influences the direction and magnitude of C, N, and P in manured and waterlogged soil cultivated with ryegrass.

Unravelling molecular fractionation of dissolved organic matter on ferrihydrite-phosphate complexes

Association of dissolved organic matter (DOM) with iron (Fe) oxyhydroxides leading to significant molecular fractionation, plays a significant role in biogeochemical cycling of carbon in soils. However, the molecular effects of coexisting phosphate, a widely distributed oxyanion in agricultural soils that has a strong affinity with Fe oxyhydroxides on such a process remain poorly understood. Here, using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) with a superiority in deciphering DOM characteristics at the molecular level, this study reveals the DOM molecular fractionation characteristics on ferrihydrite-phosphate (Fh-P) complexes. Results show that the adsorption of DOM on Fh-P complexes can be significantly inhibited by ∼50% compared to that on ferrihydrite. Optical spectroscopy and FT-ICR-MS further indicate that phosphate can greatly change the molecular fractionation of DOM on Fh-P complexes. Phosphate preferentially inhibits the highly aromatic, hydrophobic, and high molecular weight compounds (> 400 Da) of DOM on Fh-P complexes, such as condensed hydrocarbon and tannin; more CHONS compounds preferentially adsorb on the Fh-P complexes than thoseon ferrihydrite. Phosphate inhibits the adsorption of DOM with the characteristics of high oxygen atoms number, aromaticity index (AI), and double bond equivalents (DBE) on ferrihydrite. Our study demonstrates that the inhibitory effects of phosphate on the adsorption of the DOM can significantly influence the fractionation and adsorption of DOM by ferrihydrite. The findings of this work deepen our understanding of biogeochemical cycling of DOM in soil and aquifer environments.

Co-precipitation of iron and silicon: Reaction kinetics, elemental ratios and the influence of phosphorus

A sufficient supply of dissolved silicon (DSi) relative to dissolved phosphorus (DP) may decrease the likelihood of harmful algal blooms in eutrophic waters. Oxidative precipitation of Fe(II) at oxic-anoxic interfaces may contribute to the immobilization of DSi, thereby exerting control over the DSi availability in the overlying water. Nevertheless, the efficacy of DSi immobilization in this context remains to be precisely determined. To investigate the behavior of DSi during Fe(II) oxidation, anoxic solutions containing mixtures of aqueous Fe(II), DSi, and dissolved phosphorus (DP) were exposed to dissolved oxygen (DO) in the batch system. The experimental data, combined with kinetic reaction modeling, indicate that DSi removal during Fe(II) oxidation occurs via two pathways. At the beginning of the experiments, the oxidation of Fe(II)-DSi complexes induces the fast removal of DSi. Upon complete oxidation of Fe(II), further DSi removal is due to adsorption to surface sites of the Fe(III) oxyhydroxides. The presence of DP effectively competes with DSi via both of these pathways during the initial and later stages of the experiments, with as a result more limited removal of DSi during Fe(II) oxidation. Overall, we conclude that at near neutral pH the oxidation of Fe(II) has considerable capacity to immobilize DSi, where the rapid homogeneous oxidation of Fe(II)-DSi results in greater DSi removal compared to surface adsorption. Elevated DP concentration, however, effectively outcompetes DSi in co-precipitation interactions, potentially contributing to enhanced DSi availability within aquatic systems.

Kinetic and Isotherm Studies for Cu2+ and Cs+ Uptake with Mono- and Bimetallic FeO(OH)-MnOx-Clinoptilolite

This study investigates the adsorption of selected water pollutants, namely caesium and copper, by using natural zeolite of the clinoptilolite type, as well as clinoptilolites coated with MnOx, FeO(OH)-MnOx and FeO(OH). A comprehensive evaluation of these processes was conducted. The kinetics of Cs and Cu adsorption on all examined samples smoothly followed the pseudo-second-order kinetic model, with the liquid film step regarded as the slower step in both cases. The Langmuir isotherm model provided the most accurate description of Cs and Cu adsorption for all examined samples. However, when considering natural clinoptilolite and FeO(OH)-clinoptilolite systems in relation to Cu(II), the Redlich–Peterson model slightly outperformed the Langmuir model. The modification of clinoptilolite with Mn and Fe oxyhydroxides did not significantly enhance the removal efficiency of Cs compared to the unmodified sample. In contrast, the adsorption capacity, especially for MnOx-clinoptilolite, increased fourfold for Cu and other tested cations such as Pb and Zn, indicating improved efficiency in these cases.

Vallisneria spiralis Promotes P and Fe Retention via Radial Oxygen Loss in Contaminated Sediments

Microbial respiration determines the accumulation of reduced solutes and negative redox potential in organic sediments, favoring the mobilization of dissolved inorganic phosphorus (DIP), generally coprecipitated with Fe oxyhydroxides. Macrophytes releasing oxygen from the roots can contrast DIP mobility via the oxidation of anaerobic metabolism end-products. In this work, the submerged macrophyte Vallisneria spiralis was transplanted into laboratory microcosms containing sieved and homogenized organic sediments collected from a contaminated wetland. Sediments with and without plants were incubated under light and dark conditions for oxygen and DIP fluxes measurements and pore water characterization (pH, oxidation-reduction potential, DIP, dissolved Mn, and Fe). Bare sediments were net DIP sources whereas sediments with V. spiralis were weak DIP sources in the dark and large sinks in light. V. spiralis radial oxygen loss led to less negative redox potential and lower Fe, Mn, and DIP concentrations in pore water. Roots were coated by reddish plaques with large amounts of Fe, Mn, and P, exceeding internal content. The results demonstrated that at laboratory scale, the transplant of V. spiralis into polluted organic sediments, mitigates the mobility of DIP and metals through both direct and indirect effects. This, in turn, may favor sediment colonization by less-tolerant aquatic plants. Further in situ investigations, coupled with economic analyses, can evaluate this potential application as a nature-based solution to contrast eutrophication.

Cooperative roles of phosphate and dissolved organic matter in inhibiting ferrihydrite transformation and their distinct fates

Phosphate and dissolved organic matter (DOM) mediate the crystalline transformation of ferrihydrite catalyzed by Fe(II) in subsurface environments such as soils and groundwater. However, the cooperative mechanisms underlying the mediation of phosphate and DOM in crystalline transformation of ferrihydrite and the feedback effects on their own distribution and speciation remain unresolved. In this study, solid characterization indicates that phosphate and DOM can collectively inhibit the crystalline transformation of ferrihydrite to lepidocrocite and thus goethite, via synergetic effects of inhibiting recrystallization and electron transfer. Phosphate can be retained on the surface or transformed to a nonextractable form within Fe oxyhydroxides; DOM is either released into the solution or preserved in an extractable form, while it is not incorporated or retained in the interior. Element distribution and DOM composition analysis on Fe oxyhydroxides reveals even distribution of phosphate on the newly formed Fe oxyhydroxides, while the distribution of DOM depends on its specific species. Electrochemical and dynamic force spectroscopic results provide molecular-scale thermodynamic evidence explaining the inhibition of electron transfer between Fe(II) and ferrihydrite by phosphate and DOM, thus influecing the crystalline transformation of ferrihydrite and the distribution of phosphate and DOM. This study provides new insights into the coupled biogeological cycle of Fe with phosphate and DOM in aquatic and terrestrial environments.

Effect of Fe(II) on manganese removal in biofilters: Microbial community, formation of manganese oxide and related mechanisms

In this study, different concentrations of Fe(II) (0, 1.00, 7.00 mg/L) were introduced to investigate the effect on the removal of Mn(II) in the biofilter. Fe(II) significantly inhibited the removal of Mn and prolonged the start-up of biofilters, the start-up periods for the biofilters with different Fe(II) concentrations (0, 1.00 and 7.00 mg/L) were 24, 30 and 46 days, respectively. The study showed that Fe(II) and the Fe(III) oxyhydroxides generated from Fe(II) oxidation inhibited the removal of Mn(II) by affecting the proliferation of manganese-oxidizing bacteria (MnOB) and the activity of manganese oxides (MnOx) in the biofilter. On day 20, the total MnOB genera proportions were 13.44 %, 13.35 % and 20.09 % with different Fe(II) concentrations (0, 1.00, 7.00 mg/L), respectively. The addition of Fe(II) significantly impeded the proliferation of Pseudomonas, Acinetobacter and Arthrobacter, but enhanced the proliferation of Hyphomicrobium and Sphingopyxis. On day 60, the abundance of total MnOB was reduced obviously in three biofilters (6.95 %, 6.44 % and 9.76 %). This indicated that the biological oxidation of Mn dominates during the initial operation stage of the filter layer, while the chemical auto-catalytic oxidation of active MnOx dominates in the later stages. The contribution of Mn removal by biological oxidation was positively correlated with the abundance of MnOB, and batch experiments confirmed this conclusion. Moreover, the addition of Fe(II) reduced MnOx activity by suppressing the production of high-reactivity intermediate-Mn(III), and Fe(III) oxyhydroxides hindered the formation of mature MnOx films on the surface of the filter media.